CN1940143A - Production of metal material by composite compound - Google Patents
Production of metal material by composite compound Download PDFInfo
- Publication number
- CN1940143A CN1940143A CNA200510019502XA CN200510019502A CN1940143A CN 1940143 A CN1940143 A CN 1940143A CN A200510019502X A CNA200510019502X A CN A200510019502XA CN 200510019502 A CN200510019502 A CN 200510019502A CN 1940143 A CN1940143 A CN 1940143A
- Authority
- CN
- China
- Prior art keywords
- electrolysis
- chemical compound
- metal
- complex chemical
- described methods
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
This invention relates to a method of preparing metal material using complex compounds. Electrolysis is carried out in the electrolyte under the protection of inert gas or air containing M3Y with composite compounds of M1M2X combine with the collector as a cathode and carbon, metal or conductive ceramic as anode. Controlling electrolysis voltage, so that M2 reduction reaction is the dominated reaction, and M1 and X is partly or all dissolved in the electrolyte as electrolysis going on. When M1 is H, M1 can be reduced to gas leaving away the cathode. At the end of electrolys, M2 alone or with part of the M1 and X-stay is left on the cathode, which is the corresponding metal. Since M1X part or all leave away cathode in this invention during electrolysis process, the reactivity and ability of cathode is enhanced, the reaction rate and the current efficiency are effectively improved and energy consumption is reduced.
Description
Technical field
The present invention relates to a kind ofly prepare the method for metallic substance, belong to electrometallurgy and novel material and new preparation technology field thereof by complex chemical compound.
Background of invention
Materials such as metal, semi-metal, alloy, intermetallic compound are mainly produced by the method for carbon or metallic high temperature thermal reduction and high melt at present and are prepared, this method in the smelting of iron and steel, titanium, niobium, tantalum and some alloy materials by industrial application, but this class methods temperature of reaction height, very high to equipment and matching requirements, and energy consumption is huge, seriously polluted, along with the pay attention to day by day to the energy and environmental problem, the new technology that develops new less energy-consumption less contamination is very urgent.
Materials such as some metal, semi-metal, alloy, intermetallic compound also can be by electrolytic method preparation, as the industrial preparation of aluminium, magnesium, copper, nickel, lead etc.But the electrolysis process in the aqueous solution can't prepare the active metal because of the influence of the cathodic reduction that is subjected to water, and fused salt electrolysis is owing to reasons such as negative electrode dendritic growth are difficult to the industrial preparation high-melting point metal.
More than two kinds of methods prepared be block materials mostly.
Powder metallurgy technology is material preparation and the moulding new technology that a kind of raw material can efficiently be utilized, and metal, alloy powder material are the requisite raw materials of powder metallurgy.On the other hand, small sized metallic, alloy, non-metering complex chemical compound powder also have extremely important application in field of functional materials such as magneticsubstance, catalytic material, energy and material, information materials.Therefore directly has good application prospects from compound metal, alloy, intermetallic compound powder.
Patent " fused salt electrolysis of the oxygen in metal oxide and the sosoloid is removed " (PCT/GB99/01781) discloses a kind of at high-temperature fusant M
3Be lower than under the decomposition voltage of fused salt solid metal oxide M among the Y
2The method that obtains clean metal at negative electrode is removed in oxygen electrolysis in X or the metal oxygen solid solution; On this basis, patent " intermetallic compound " (PCT/GB01/05034) discloses and utilizes above method to slough the method that non-metallic element X obtains intermetallic compound in the solid state cathode that element constitutes more than three kinds and three kinds by containing; Patent " manufacturing of metal and powdered alloy and powder " (PCT/GB01/05031) discloses thus, and method obtains metal and powdered alloy and technology thereof after removing non-metallic element.But this method is the positively charged ion M in the fused salt in cathode reduction process
3Can be in negative electrode combine with negative electrode or cathodic reduction product and block the ion migration passage and reduce mass-transfer efficiency, cause electrolytic efficiency and current efficiency lower, the energy consumption increase.
Summary of the invention
Different with existing method, at its deficiency, the invention provides and a kind ofly prepare the method for metallic substance by complex chemical compound, this method speed of response and current efficiency are higher, and energy consumption is lower.
Technical scheme provided by the invention is: a kind ofly prepare the method for metallic substance by complex chemical compound, with complex chemical compound M
1M
2X contains M as negative electrode and carbon, metal or conductivity ceramics anode with the collector combination under protection of inert gas or in the air
3Carry out electrolysis in the electrolytic solution of Y, the control electrolysis voltage makes it mainly to take place M
2Reduction reaction, M
1Then partly or entirely be dissolved in the electrolytic solution with X, work as M along with electrolytic
1During for H, M
1Thereby also can be reduced to gas and leave negative electrode, electrolysis finishes M
2Separately or with part M
1Stay on the negative electrode with X, promptly obtain the corresponding metal material; M wherein
1Be selected from Ca, Mg, Ba, Li, Na, K, one or more among the H; M
2Be Ti, Zr, Hf, Cr, Mo, W, V, Nb, Ta, Fe, Co, Ni, Mn, Cu, Zn, Si, Ge, Pb, Sn, Ag, Au, Pt, Pd, Rh, Ir, Ru, Os, Re, Al, B, Ga, In, Tl, Sc, Y, U, group of the lanthanides, one or more in the actinium series; M
3Be Li, Na, K, Rb, Cs, Be, Ca, Mg, Ba, monatomic positively charged ion of Sr or R
1R
2R
3R
4N or R
1R
2R
3R
4P polyatom positively charged ion or two or more the mixed system among them, R
1, R
2, R
3, R
4Be respectively the organic group or the H that contain 1-16 carbon atom; X is B, C, N, O, S, P, F, Cl, Br, the group monatomic or two or more composition among them of I; Y is F, Cl, monatomic negatively charged ion or the NO of Br
3, OH, SO
4, AlCl
3, PF
6, BF
4, SbF
6, CH
3COO, CF
3SO
3, (CF
3SO
2)
3N, (CF
3SO
2)
3The polyatom negatively charged ion of C, or two or more mixed system among them.
M wherein
1M
2X contains M by two or more
1And M
2Relative simple compounds in heating (temperature), radiation (light, ultrasonic wave etc.), mix reaction generation in air, inert atmosphere, vacuum or liquid medium under the conditions such as (magnetic stirrings, ball millings etc.), also can by electricity embedding, electro-adsorption, electrolysis from etc. the field electrochemical reaction generate, or be natural mineral and industrial raw material and waste material.The particle size of complex chemical compound is 0.01-100 μ m.
The complex chemical compound particulate becomes piece and the compound formation composite cathode of electrical conductor through cast or compressing tablet.The pressure of preparation compressing tablet is 0-30MPa, and sintering temperature is lower than the decomposition temperature of complex chemical compound, between the 30-80% of the fusing point of complex chemical compound.
Complex chemical compound is that face contacts, the some contact contacts with netted with the combination of electrical conductor.
Above-mentioned electrolysis temperature is-30-1000 ℃, and electrolytic process applies voltage 0.5-5V.
Electrolytic solution M
3Y is acid, alkali, salt brine solution, 0 to 150 ℃ of electrolysis temperature.
Electrolytic solution M
3Y is organic solvent or the room temperature fused salt (ionic liquid) that is added with supporting electrolyte, and electrolysis temperature is-30 to 200 ℃.
Electrolytic solution M
3The melting salt that Y forms for one or more inorganic salt, electrolysis temperature is 200 to 1000 ℃ of temperature.
M
1The mode that X leaves negative electrode comprises dissolving or generates gas to be separated out.
Above-mentioned electric degradation production is pure metal, semi-metal, alloy or intermetallic compound; Its granular size is 1nm-50 μ m.
Electrolysate is retained to room temperature after taking out in rare gas element or air from electrolytic solution, and water or organic solvent thorough washing.
The present invention will contain metal or metalloid M
1And M
2Complex chemical compound be negative electrode, decompose complex chemical compound by electricity and prepare metal, semi-metal, alloy, inter-metallic compound material, M wherein
1Follow electrolytic carrying out partly or entirely to leave negative electrode, thereby improve the duct that cathode ion transports, simultaneously because M
1Leave away and also strengthened M
2Reducing activity, so can significantly shorten electrolysis time, improve current efficiency and cut down the consumption of energy.
The present invention possesses following characteristics:
(1) all raw materials are simple compounds or natural mineral, and the source is abundant;
(2) process is simple, implements easily, and processing parameter is easy to control;
(3) can conveniently prepare various metals, semi-metal, alloy, intermetallic compound powder metallurgical raw material and functional materials;
(4) owing to M in the electrolytic process
1X partly or entirely leaves negative electrode, has improved cathodic reaction activity and ability, effectively improves speed of response and current efficiency, has reduced energy consumption, has overcome the deficiencies in the prior art.
(5) method provided by the present invention not only is suitable for high-temperature molten salt, also is suitable for the metal or alloy powder of preparation nano-scale under near the low temperature room temperature or more.
Description of drawings:
Fig. 1 is the stereoscan photograph and the X-ray diffraction spectrum of uhligite;
Fig. 2 is stereoscan photograph and X-ray energy spectrum analytical results with uhligite electrolysate shown in Figure 1.
Embodiment
The present invention adopts two or more to contain M
1And M
2Relative simple compounds in heating (temperature), radiation (light, ultrasonic wave etc.), mix under the conditions such as (magnetic stirrings, ball millings etc.) reaction generation M in air, inert atmosphere, vacuum or liquid medium
1M
2X, also can by electricity embedding, electro-adsorption, electrolysis from etc. the field electrochemical reaction generate M
1M
2X or directly take from natural mineral and industrial raw material and waste material; As required with the M of gained
1M
2X is ground to the microparticle that particle diameter is 0.01-100 μ m, with M
1M
2The X particulate becomes piece through cast or compressing tablet, makes it to possess exercisable physical strength 25-1500 ℃ of sintering temperature moulding as required; With M
1M
2X blocks of solid and metallic conductor are connected to form negative electrode; This negative electrode and the metal that is complementary with electrolytic solution and electrolysis temperature, pottery or carbon annode placed contain M
3The voltage that applies 0.5-5V in the electrolytic solution of Y carries out electrolysis.According to the length of height that applies voltage and electrolysis time, M
1X partly or entirely leaves negative electrode, stays M at negative electrode
2(metal, alloy, intermetallic compound, semi-metal).
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
The Ca (OH) of mol ratio such as get
2And TiO
2, add an amount of distilled water, with the speed ball milling 2-5h of planetary ball mill, make it thorough mixing with 200-300 commentaries on classics/min.After the paste mixture oven dry that mixes, get the 2-3g powder with 2-10MPa pressure compression molding.Compressing tablet at 900-1200 ℃ of sintering 2-10h, is promptly obtained porous CaTiO
3(particle diameter 0.5-3 μ m sees accompanying drawing 1).CaCl at 850-950 ℃
2In the fused salt, be protection gas, with Mo silk or Mo net parcel CaTiO with the argon gas
3Compressing tablet is anode as composite cathode with graphite, applies 3.0V voltage, and electrolysis 6h takes out washing with product cooling back, can obtain the metal Ti (particle diameter 2-10 μ m sees accompanying drawing 2) that oxygen level is lower than 2000ppm.Electrolysis TiO under the same terms
2Obtaining equifinality need be above 10 hour.
Embodiment 2
Get steel climbing high slag and (mainly contain Ca, Mg, Si, Ti, Fe, S, elements such as O) or ilmenite concentrate (mainly contain Ca, Mg, Si, Ti, V, Fe, S, elements such as O) 1.5-2.0g, it is ground to granular size is about 0.5-10 μ m, behind 2-10MPa pressure compression molding, at 800-1000 ℃ of sintering 2h.CaCl at 850-950 ℃
2In the fused salt, be protection gas, wrap up the blast furnace slag compressing tablet as composite cathode with Mo silk or Mo net with the argon gas; with the graphite rod is anode, applies 3.0-3.2V voltage, electrolysis 6-15h; washing is taken out in product cooling back, can obtain TiFeSi powdered alloy (the about 10-20 μ of particle diameter m).
Embodiment 3
Get microlite (CaNaTa
2O
6(OH)) 100g places planetary ball mushroom machine to grind, and crosses 300 mesh sieves, gets the 6MPa compression moulding of 2g sample, and is in 900 ℃ of sintering 2h that it and molybdenum net is compound as negative electrode, is anode with graphite, at 700 ℃ CaCl
2Apply 2.9-3.3V voltage electrolysis 6 hours in the-NaCl fused salt, sample is taken out in the cooling back, and after water and Diluted Acid Washing, obtaining granularity is the tantalum powder of hundreds of nanometer.
Embodiment 4
Get sheelite (CaWO
4) 100g, place planetary ball mushroom machine to be ground to the about 10-90 μ of particle diameter m, get the 4MPa compression moulding of 2g sample, in 900 ℃ of sintering 2h that it and molybdenum net is compound as negative electrode, be anode with graphite, at 600 ℃ CaCl
2Apply 2.9-3.3V voltage electrolysis 8 hours in the-NaCl fused salt, sample is taken out in the cooling back, after water and Diluted Acid Washing, obtains the tungsten powder that granularity is 100-1000nm.
Embodiment 5
Get Na
2WO
4About 2.0g is behind the compression molding, at 550-600 ℃ of sintering 2h.LiCl-NaCl-CaCl at 580-620 ℃
2In the fused salt mixt, being protection gas with the argon gas, wrapping up the ilmenite concentrate compressing tablet as composite cathode with Mo silk or Mo net, is anode with the graphite rod, applies 3.1-3.3V voltage, and electrolysis 6-12h takes out washing with product cooling back, can obtain the W powder.
Embodiment 6
In 10-80 ℃ phosphofluoric acid methyl butyl imidazole ion liquid, small amount of solid state Platinic chloride machinery covered be pressed onto on the platinized platinum as negative electrode, with the platinized platinum is anode, apply 1.0-3V voltage, electrolysis 0.5-5h, on the negative electrode nickel foam, promptly obtain the simple substance platinum of 2-100nm size, simultaneously at the negative electrode bubbing.
Embodiment 7
With etc. the Zn (NO of mol ratio
3)
26H
2O and Ca (NO
3)
24H
2O is dissolved in an amount of distilled water, slowly is added to while stirring in the excessive KOH solution.Dropwise the back and continue to stir 12-48h, filter, washing, drying obtains Ca[Zn (OH)
3]
22H
2O.At room temperature, get about 0.5g Ca[Zn (OH)
3]
22H
2O machinery covers and is pressed onto about 0.5cm
2As composite cathode, be anode with the platinized platinum on the nickel foam, in 10-30% (mass percent) KOH electrolysis of solutions liquid, apply 1.5-2V voltage under the room temperature, electrolysis 0.5-3h promptly obtains simple substance Zn powder on the negative electrode nickel foam.
Claims (9)
1. one kind prepares the method for metallic substance by complex chemical compound, it is characterized in that: with complex chemical compound M
1M
2X contains M as negative electrode and carbon, metal or conductivity ceramics anode with the collector combination under protection of inert gas or in the air
3Carry out electrolysis in the electrolytic solution of Y, the control electrolysis voltage makes it mainly to take place M
2Reduction reaction, M
1Then partly or entirely be dissolved in the electrolytic solution with X, work as M along with electrolytic
1During for H, M
1Thereby also can be reduced to gas and leave negative electrode, electrolysis finishes M
2Separately or with part M
1Stay on the negative electrode with X, promptly obtain the corresponding metal material; M wherein
1Be selected from Ca, Mg, Ba, Li, Na, K, one or more among the H; M
2Be Ti, Zr, Hf, Cr, Mo, W, V, Nb, Ta, Fe, Co, Ni, Mn, Cu, Zn, Si, Ge, Pb, Sn, Ag, Au, Pt, Pd, Rh, Ir, Ru, Os, Re, Al, B, Ga, In, Tl, Sc, Y, U, group of the lanthanides, one or more in the actinium series; M
3Be Li, Na, K, Rb, Cs, Be, Ca, Mg, Ba, monatomic positively charged ion of Sr or R
1R
2R
3R
4N or R
1R
2R
3R
4P polyatom positively charged ion or two or more the mixed system among them, R
1, R
2, R
3, R
4Be respectively the organic group or the H that contain 1-16 carbon atom; X is B, C, N, O, S, P, F, Cl, Br, the group monatomic or two or more composition among them of I; Y is F, Cl, monatomic negatively charged ion or the NO of Br
3, OH, SO
4, AlCl
3, PF
6, BF
4, SbF
6, CH
3COO, CF
3SO
3, (CF
3SO
2)
3N, (CF
3SO
2)
3The polyatom negatively charged ion of C, or two or more mixed system among them.
2. according to the described method of claim 1, it is characterized in that: electrolysis temperature is-30-1000 ℃, and electrolytic process applies voltage 0.5-5V.
3. according to the described method of claim 1, it is characterized in that: the particle size of complex chemical compound is 0.01-100 μ m.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that: complex chemical compound is the complex chemical compound of natural mineral or synthetic.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that: the complex chemical compound particulate becomes piece and the compound formation composite cathode of electrical conductor through cast or compressing tablet.
6. according to claim 1 or 2 or 3 described methods, it is characterized in that: electric degradation production is a pure metal.
7. according to claim 1 or 2 or 3 described methods, it is characterized in that: electric degradation production is alloy or intermetallic compound.
8. according to claim 1 or 2 or 3 described methods, it is characterized in that: electric degradation production is a semi-metal.
9. according to claim 1 or 2 or 3 described methods, it is characterized in that: the granular size of products therefrom is 1nm-50 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510019502XA CN100570011C (en) | 2005-09-28 | 2005-09-28 | A kind of method for preparing metallic substance by complex chemical compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510019502XA CN100570011C (en) | 2005-09-28 | 2005-09-28 | A kind of method for preparing metallic substance by complex chemical compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1940143A true CN1940143A (en) | 2007-04-04 |
| CN100570011C CN100570011C (en) | 2009-12-16 |
Family
ID=37958660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510019502XA Expired - Fee Related CN100570011C (en) | 2005-09-28 | 2005-09-28 | A kind of method for preparing metallic substance by complex chemical compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100570011C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979715A (en) * | 2010-12-01 | 2011-02-23 | 武汉大学 | Method for preparing silicon-calcium alloy |
| CN102230194A (en) * | 2011-07-26 | 2011-11-02 | 武汉大学 | Method for preparing nano-tungsten powder from calcium tungstate |
| CN101597776B (en) * | 2009-07-07 | 2012-04-25 | 武汉大学 | Metallurgy method of metal sulfide M1S |
| CN105525184A (en) * | 2015-12-29 | 2016-04-27 | 常熟市良益金属材料有限公司 | High-nickel alloy ultrasonic flaw detection tube |
| CN105839146A (en) * | 2016-04-01 | 2016-08-10 | 宁夏邦鼎材料与环保科技有限公司 | Silicon-germanium solid solution and preparation method and application thereof |
| CN110760884A (en) * | 2019-11-06 | 2020-02-07 | 南通冠达粉末冶金有限公司 | Preparation process of powder metallurgy auxiliary material |
-
2005
- 2005-09-28 CN CNB200510019502XA patent/CN100570011C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597776B (en) * | 2009-07-07 | 2012-04-25 | 武汉大学 | Metallurgy method of metal sulfide M1S |
| CN101979715A (en) * | 2010-12-01 | 2011-02-23 | 武汉大学 | Method for preparing silicon-calcium alloy |
| CN101979715B (en) * | 2010-12-01 | 2012-09-05 | 武汉大学 | Method for preparing silicon-calcium alloy |
| CN102230194A (en) * | 2011-07-26 | 2011-11-02 | 武汉大学 | Method for preparing nano-tungsten powder from calcium tungstate |
| CN105525184A (en) * | 2015-12-29 | 2016-04-27 | 常熟市良益金属材料有限公司 | High-nickel alloy ultrasonic flaw detection tube |
| CN105839146A (en) * | 2016-04-01 | 2016-08-10 | 宁夏邦鼎材料与环保科技有限公司 | Silicon-germanium solid solution and preparation method and application thereof |
| CN105839146B (en) * | 2016-04-01 | 2018-05-04 | 武汉大学 | A kind of SiGe solid solution and its preparation method and application |
| CN110760884A (en) * | 2019-11-06 | 2020-02-07 | 南通冠达粉末冶金有限公司 | Preparation process of powder metallurgy auxiliary material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100570011C (en) | 2009-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101597776B (en) | Metallurgy method of metal sulfide M1S | |
| CN1867702B (en) | For the production of the thermal and electrochemical process of metal | |
| JP6239117B2 (en) | Method for recovering discarded cemented carbide | |
| CN100570011C (en) | A kind of method for preparing metallic substance by complex chemical compound | |
| CN1837411B (en) | Method for preparing refractory active metal or alloy | |
| JP2004518810A (en) | Electrodeposition of high purity aluminum using inert anode | |
| CN1479794A (en) | Metal and alloy powers and powder fabrication | |
| KR20020091046A (en) | Cermet inert anode for use in the electrolytic production of metals | |
| CN102864468A (en) | Method for producing superfine metal powder | |
| CN101457372A (en) | Method for directly preparing titanium and titanium alloy by titanium-containing waste residue | |
| CN109763134A (en) | The preparation method of porous silicon | |
| JPS6025511B2 (en) | Electrode for molten salt electrolysis with electrocatalytic coating layer | |
| CN112391653B (en) | Method for reducing rare earth oxide into rare earth metal simple substance in chloride molten salt system | |
| CN107460503A (en) | The method that micro-nano copper powder is reclaimed from waste printed circuit board | |
| CN101603182A (en) | A kind of from oxide M 1The electrochemical method of deoxygenation among the O | |
| CN102230194B (en) | Method for preparing nano-tungsten powder from calcium tungstate | |
| CN109055997B (en) | Preparation of superfine Al by fused salt electrolysis method3Method for producing Zr intermetallic compound particles | |
| Li et al. | Electrochemical properties of powder-pressed Pb–Ag–PbO2 anodes | |
| CN1896330A (en) | Hydrogen-storage alloy, its production and use | |
| KR20050076650A (en) | Method for producing indium-containing aqueous solution | |
| CN110656257B (en) | Method for preparing nano porous gold based on titanium-based amorphous alloy | |
| CN102061489B (en) | Improved process for smelting metallic titanium by electro-deoxidation method | |
| CN108893751B (en) | Preparation method and application of titanium-based oxide | |
| CN104831306A (en) | Ultrafine silicon-based alloy powder and electrochemical preparation method thereof | |
| CN104404573A (en) | Preparation method of vanadium metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091216 Termination date: 20120928 |